8-Quinolinyl Oxazoline: Ligand Exploration in Enantioselective Ni-Catalyzed Reductive Carbamoyl-Alkylation of Alkene to Access the Chiral Oxindoles

Abstract

Chiral ligands play an essential role in transition-metal-catalyzed enantioselective transformations, in which chiral oxazoline-based scaffolds are the privileged chiral ligand. Nevertheless, 8-quinolinyl oxazoline (8-Quinox) ligands are underexplored in transition-metal-catalyzed asymmetric transformations since their development in 1998. Herein, we report an 8-Quinox ligand promoted Ni-catalyzed enantioselective reductive carbamoyl-alkylation of carbamoyl chloride tethered styrene with unactivated alkyl iodide, providing an expedient access to valuable enantioenriched oxindoles in good results.

Key words

chiral ligand - nickel catalysis - reductive coupling - dicarbofunctionalization of alkene - oxindole

Publication History

Received: 24 April 2022

Accepted after revision: 30 May 2022

Accepted Manuscript online:
30 May 2022

Article published online:
08 July 2022

• References and Notes

• 1a Feng J, Holmes M, Krische MJ. Chem. Rev. 2017; 117: 12564
• 1b Süsse L, Stoltz BM. Chem. Rev. 2021; 121: 4084
• 2 For a selected book, see: Privileged Chiral Ligands and Catalysts . Zhou Q.-L. Wiley-VCH; Weinheim: 2011
• 3a Hargaden GC, Guiry PJ. Chem. Rev. 2009; 109: 2505
• 3b Carroll MP, Guiry PJ. Chem. Soc. Rev. 2014; 43: 819
• 3c Yang G, Zhang W. Chem. Soc. Rev. 2018; 47: 1783
• 3d Connon R, Roche B, Rokade BV, Guiry PJ. Chem. Rev. 2021; 121: 6373
• 4a Brunner H, Obermann U, Wimmer P. J. Organomet. Chem. 1986; 316: C1
• 4b Brunner H, Obermann U, Wimmer P. Organometallics 1989; 8: 821

For selected examples, see:
• 5a Werner EW, Mei TS, Burckle AJ, Sigman MS. Science 2012; 338: 1455
• 5b Mei TS, Werner EW, Burckle AJ, Sigman MS. J. Am. Chem. Soc. 2013; 135: 6830
• 5c Mei TS, Patel HH, Sigman MS. Nature 2014; 508: 340
• 5d Patel HH, Sigman MS. J. Am. Chem. Soc. 2015; 137: 346
• 5e Bahamonde A, Al Rifaie B, Martín-Heras V, Allen JR, Sigman MS. J. Am. Chem. Soc. 2019; 141: 8708
• 5f Liu J, Yuan Q, Toste FD, Sigman MS. Nat. Chem. 2019; 11: 710
• 5g Ross SP, Rahman AA, Sigman MS. J. Am. Chem. Soc. 2020; 142: 10516
• 6 Nishiyama H, Sakaguchi H, Nakamura T, Horihata M, Kondo M, Itoh K. Organometallics 1989; 8: 846
• 7a Zhang L, Zuo Z.-Q, Wan X.-L, Huang Z. J. Am. Chem. Soc. 2014; 136: 15501
• 7b Chen J, Xi T, Lu Z. Org. Lett. 2014; 16: 6452
• 8 Babu SA, Krishnan KK, Ujwaldev SM, Anilkumar G. Asian J. Org. Chem. 2018; 7: 1033
• 9 Chen J, Xi T, Lu Z. Org. Chem. Front. 2018; 5: 247 ; and the references therein
• 10a Wu X.-Y, Li X.-H, Zhou Q.-L. Tetrahedron: Asymmetry 1998; 9: 4143
• 10b Wu X.-Y, Xu H.-D, Zhou Q.-L, Chan AS. C. Tetrahedron: Asymmetry 2000; 11: 1255
• 10c Li X.-G, Cheng X, Ma J.-A, Zhou Q.-L. J. Organomet. Chem. 2001; 640: 65
• 10d Wu X.-Y, Xu H.-D, Tang F.-Y, Zhou Q.-L. Tetrahedron: Asymmetry 2001; 12: 2565
• 10e Li Z.-P, Wu X.-Y, Zhou Q.-L, Chan W.-L. Chin. J. Chem. 2001; 19: 40
• 10f Zhou Y.-B, Tang F.-Y, Xu H.-D, Wu X.-Y, Ma J.-A, Zhou Q.-L. Tetrahedron: Asymmetry 2002; 13: 469
• 11a Lu P, Ren X, Xu H, Lu D, Sun Y, Lu Z. J. Am. Chem. Soc. 2021; 143: 12433
• 11b Ren X, Lu Z. Org. Lett. 2021; 23: 8370

For selected reviews and examples, see:
• 12a Singh GS, Desta ZY. Chem. Rev. 2012; 112: 6104
• 12b Galliford CV, Scheidt KA. Angew. Chem. Int. Ed. 2007; 46: 8748
• 12c Trost BM, Brennan MK. Synthesis 2009; 18: 3003
• 12d Huters AD, Styduhar ED, Garg NK. Angew. Chem. Int. Ed. 2012; 51: 3758
• 12e Kato H, Yoshida T, Tokue T, Nojiri Y, Hirota H, Ohta T, Williams RM, Tsukamoto S, Notoamides A.-D. Angew. Chem. Int. Ed. 2007; 46: 2254

For selected reviews and examples, see:
• 13a Cao Z.-Y, Zhou F, Zhou J. Acc. Chem. Res. 2018; 51: 1443
• 13b Ping Y, Li Y, Zhu J, Kong W. Angew. Chem. Int. Ed. 2019; 58: 1562
• 13c Marchese AD, Larin EM, Mirabi B, Lautens M. Acc. Chem. Res. 2020; 53: 1605
• 13d Hu HZ, Teng F, Liu J, Hu WM, Luo S, Zhu Q. Angew. Chem. Int. Ed. 2019; 58: 9225
• 13e Bai X, Wu C, Ge S, Lu Y. Angew. Chem. Int. Ed. 2020; 59: 2764

For selected reviews and examples, see:
• 14a Wang K, Ding Z, Zhou Z, Kong W. J. Am. Chem. Soc. 2018; 140: 12364
• 14b Jin Y, Wang C. Angew. Chem. Int. Ed. 2019; 58: 6722
• 14c Tian Z.-X, Qiao J.-B, Xu G.-L, Pang X, Qi L, Ma W.-Y, Zhao Z.-Z, Duan J, Du Y.-F, Su P, Liu X.-Y, Shu X.-Z. J. Am. Chem. Soc. 2019; 141: 7637
• 14d Peng Y, Wang K, Pan Q, Ding Z, Zhou Z, Guo Y, Kong W. ACS Catal. 2019; 9: 7335
• 14e Li Y, Ding Z, Lei A, Kong W. Org. Chem. Front. 2019; 6: 3305
• 14f Ma T, Chen Y, Li Y, Ping Y, Kong W. ACS Catal. 2019; 9: 9127
• 14g Jin Y, Yang H, Wang C. Org. Lett. 2019; 21: 7602
• 14h Jin Y, Wang C. Chem. Sci. 2019; 10: 1780
• 14i He J, Xue Y, Han B, Zhang C, Wang Y, Zhu S. Angew. Chem. Int. Ed. 2020; 59: 2328
• 14j Fan P, Lan Y, Zhang C, Wang C. J. Am. Chem. Soc. 2020; 142: 2180
• 14k Chen X.-W, Yue J.-P, Wang K, Gui Y.-Y, Niu Y.-N, Liu J, Ran C.-K, Kong W, Zhou W.-J, Yu D.-G. Angew. Chem. Int. Ed. 2021; 60: 14068
• 14l Qiao J.-B, Zhang Y.-Q, Yao Q.-W, Zhao Z.-Z, Peng X, Shu X.-Z. J. Am. Chem. Soc. 2021; 143: 12961
• 14m Wu J, Wang C. Org. Lett. 2021; 23: 6407
• 15 Lan Y, Wang C. Commun. Chem. 2020; 3: 45
• 16a Wu X, Qu J, Chen Y. J. Am. Chem. Soc. 2020; 142: 15654
• 16b Wu X, Luan B, Zhao W, He F, Wu X.-Y, Qu J, Chen Y. Angew. Chem. Int. Ed. 2022; in press
• 16c Wu X, Shrestha M, Chen Y. Synlett 2021; 32: 955
• 16d He Y, Zhu S. Chin. J. Org. Chem. 2020; 40: 4377
• 16e Shrestha M, Wu X, Huang W, Qu J, Chen Y. Org. Chem. Front. 2021; 8: 4024
• 17a Fang K, Huang W, Shan C, Qu J, Chen Y. Org. Lett. 2021; 23: 5523
• 17b Huang W, Shrestha M, Wang C, Fang K, Teng Y, Qu J, Chen Y. Org. Chem. Front. 2021; 8: 4106
• 17c Xi Y, Wang C, Zhang Q, Qu J, Chen Y. Angew. Chem. Int. Ed. 2021; 60: 2699
• 18 General Procedure To a dried 8 mL vial were added ligand (22 mol%), Mn (2.0 equiv), Ni(ClO₄)₂ ·6H₂O (15 mol%), and carbamoyl chloride (1.0 equiv) (if solid). Then the vial was transferred into glovebox. LiBr (1.0 equiv), NMP (0.2 M), carbamoyl chloride (1.0 equiv) (if liquid), and alkyl halide (3.0 equiv) were added in sequence inside the glovebox. The vial was then put into the glovebox and stirred for the needed time. After completion, the reaction mixture was quenched with H₂O, filtered through a pad of Celite, and extracted with EtOAc for three times. The resulted filtrate was separated. The combined organic phase was washed with brine and concentrated under reduced pressure to yield the crude product, which was purified by silica gel flash column chromatography to afford products 3. (S)-1,3-Dimethyl-3-octylindolin-2-one (3a) Pale yellow oil (31.6 mg, 58%); R_f = 0.56 (PE/EtOAc = 10:1); [α]_D ²³ + 7.90 (c = 1.67, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 7.26 (td, J = 8.0, 1.2 Hz, 1 H), 7.16 (dd, J = 7.2, 0.8 Hz, 1 H), 7.06 (td, J = 7.6, 0.8 Hz, 1 H), 6.84 (d, J = 7.6 Hz, 1 H), 3.21 (s, 3 H), 1.88 (td, J = 12.4, 4.8 Hz, 1 H), 1.71 (td, J = 12.4, 4.4 Hz, 1 H), 1.34 (s, 3 H), 1.25–1.14 (m, 10 H), 1.00–0.77 (m, 5 H). ¹³C NMR (100 MHz, CDCl₃): δ = 181.0, 143.5, 134.5, 127.7, 122.6, 122.5, 108.0, 48.6, 38.7, 31.9, 29.9, 29.4, 29.3, 26.2, 24.6, 23.9, 22.7, 14.2. HRMS (ESI): m/z calcd for C₁₈H₂₈NO⁺: 274.2165; found: 274.2157. HPLC (Chiralpak IC): n-hexane/i-PrOH = 90:10, flow rate 1.0 mL/min, λ = 254 nm, t _R = 6.551 min (major), t _R = 8.110 min (minor); 96:4 e.r. (S)-1-Benzyl-3-methyl-3-octylindolin-2-one (3b) Pale yellow oil (38.1 mg, 55%); R_f = 0.77 (PE/EtOAc = 10:1); [α]_D ²³ + 10.30 (c = 0.66, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 7.29–7.23 (m, 5 H), 7.12 (dd, J = 16.8, 7.8 Hz, 2 H), 7.00 (t, J = 7.2 Hz, 1 H), 6.69 (d, J = 7.6 Hz, 1 H), 4.97 (d, J = 15.6 Hz, 1 H), 4.82 (d, J = 15.6 Hz, 1 H), 1.93 (td, J = 12.0, 2.8 Hz, 1 H), 1.74 (td, J = 12.8, 3.2 Hz, 1 H), 1.38 (s, 3 H), 1.23–1.13 (m, 12 H), 0.82 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 181.1, 142.5, 136.3, 134.4, 128.8, 127.6, 127.4, 122.7, 122.5, 109.1, 48.6, 43.7, 38.7, 31.9, 29.9, 29.4, 29.3, 24.8, 24.3, 22.7, 14.2. HRMS (ESI): m/z calcd for C₂₄H₃₂NO⁺: 350.2478; found: 350.2470. HPLC (Chiralpak IC): n-hexane/i-PrOH = 90:10, flow rate 1.0 mL/min, λ = 254 nm, t _R = 5.739 min (major), t _R = 6.239 min (minor); 95.5:4.5 e.r. (S)-1,3-Dimethyl-3-octyl-6-(trifluoromethyl)indolin-2-one (3c) Pale yellow oil (30.7 mg, 45%); R_f = 0.65 (PE/EtOAc = 10:1); [α]_D ²³ + 13.76 (c = 2.95, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 7.27 (d, J = 7.2 Hz, 1 H), 7.18 (d, J = 7.6 Hz, 1 H), 6.96 (s, 1 H), 3.17 (s, 3 H), 1.83 (td, J = 12.0, 3.2 Hz, 1 H), 1.66 (td, J = 12.0, 3.6 Hz, 1 H), 1.28 (s, 3 H), 1.17–1.07 (m, 12 H), 0.76 (t, J = 6.4 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 180.6, 144.1, 138.4, 130.2 (q, J _C–F = 32.3 Hz), 124.1 (q, J _C–F = 270.2 Hz), 122.7, 119.6 (q, J _C–F = 3.8 Hz), 104.6 (q, J _C–F = 3.7 Hz), 48.7, 38.5, 31.9, 29.8, 29.3, 29.3, 26.4, 24.6, 23.7, 22.7, 14.2. ¹⁹F NMR (376 MHz, CDCl₃): δ = –62.3; HRMS (ESI): m/z calcd for C₁₉H₂₇F₃NO⁺: 342.2039; found: 342.2030. HPLC (Chiralpak IC): n-hexane/i-PrOH = 90:10, flow rate 1.0 mL/min, λ = 254 nm, t _R = 4.627 min (major), t _R = 5.098 min (minor); 95.5:4.5 e.r. ( S )-1,3-Dimethyl-3-propylindolin-2-one (3d) Pale yellow oil (29.7 mg, 73%); R_f = 0.42 (PE/EtOAc = 10:1); [α]_D ²³ +15.04 (c = 2.78, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 7.26 (t, J = 8.0 Hz, 1 H), 7.17 (d, J = 7.2 Hz, 1 H), 7.06 (t, J = 7.6 Hz, 1 H), 6.83 (d, J = 7.2 Hz, 1 H), 3.21 (s, 3 H), 1.88 (td, J = 12.4, 4.4 Hz, 1 H), 1.70 (td, J = 12.0, 4.0 Hz, 1 H), 1.35 (s, 3 H), 1.05–0.96 (m, 1 H), 0.90–0.83 (m, 1 H), 0.77 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 181.0, 143.4, 134.4, 127.7, 122.6, 122.5, 107.9, 48.6, 40.9, 26.2, 23.8, 17.9, 14.3. HRMS (ESI): m/z calcd for C₁₃H₁₈NO⁺: 204.1383; found: 204.1378. HPLC (Chiralpak IC): n-hexane/i-PrOH = 90:10, flow rate 1.0 mL/min, λ = 254 nm, t _R = 7.967 min (major), t _R = 8.377 min (minor); 91.5:8.5 e.r.